Method of finishing synthetic organic fibrous material, in particular of providing it with an antistatic finish

ABSTRACT

A method of finishing synthetic organic fibrous material, in particular of providing such material with an antistatic finish and simultaneously improving the dirt repellency is provided, which comprises treating said material with aqueous or organic solutions or emulsions which contain (a) at least one copolymer derived from at least two of the monomers of formulae ##STR1## wherein R is straight-chain or branched alkyl of 1 to 8 carbon atoms, R 1  is hydrogen or methyl, R 2  is alkyl of 1 to 6 carbon atoms, m is an integer from 6 to 15, and each of r and s is 1 or 2, or a copolymer of the above monomers and further ethylenically unsaturated monomers, optionally in admixture with further homo- or copolymers and/or monomeric compounds. The furnish synthetic organic fibrous material, especially textile material, shows a permanent antistatic effect. The antisoiling effect and also the fastness to rubbing and light and the soft handle are not impared by the finish.

This is a division of application Ser. No. 639,312, filed on Dec. 10,1975, now U.S. Pat. No. 4,066,597, patented Jan. 3, 1978.

It is known to provide synthetic organic fibrous material with anantistatic or also dirt repellent finish. It is also known that a markeddeterioration of the antisoiling effect occurs in many antistaticfinishes. A further frequently observed disadvantage is the poorresistance to yellowing on exposure to light and/or heat.

To overcome these disadvantages in large measure it is the object of thepresent invention to provide preparations or compositions withantistatic properties for appropriate finishing procedures.

The present invention therefore provides a method of finishing syntheticorganic fibrous material, in particular of providing such material withan antistatic finish and simultaneously improving the dirt repellency,which comprises treating said material with aqueous or organic solutionsor emulsions which contain

(a) at least one copolymer derived from at least two of the monomers offormulae ##STR2## wherein R is straight-chain or branched alkyl of 1 to8 carbon atoms, R₁ is hydrogen or methyl, R₂ is alkyl of 1 to 6 carbonatoms, m is an integer from 6 to 15, and each of r and s is 1 or 2, or acopolymer of the above monomers and further ethylenically unsaturatedmonomers, optionally in admixture with at least one of the components

(b₁) a homopolymer derived from the monomers of formulae (1) to (3),

(b₂) a further homopolymer or copolymer,

(b₃) a compound of formula ##STR3## wherein R' is straight-chain orbranched alkyl of 1 to 18 carbon atoms, R₁ is hydrogen or methyl, R₂ 'is hydrogen or C_(n) H_(2n+1) and n is an integer from 1 to 24, and

(b₄) a compound of formula ##STR4## in which A is --CH₂ CH₂ --, ##STR5##R₃ ' is hydrogen or C_(n) H_(2n+1) - and n is an integer from 1 to 24,and subsequently drying it at elevated temperature.

It is also a further object of the invention to provide the preparationsfor carrying out the method of application.

The homopolymers and copolymers (a), (b₁) and (b₂) can have molecularweights of about 2000 to 50,000.

The monomers of formulae (1) to (3) are known compounds. The compoundsof formula (1) are known, for example, from Swiss patent 445,126 andGerman Offenlegungsschrift 2,215,434 (N-phosphonomethylacrylic amides),the compounds of formula (2) from German Auslegeschrift 1,111,825, andthe compounds of formula (3) from U.S. Pat. No. 2,839,430.

It is preferred to use copolymers or mixtures of copolymers derived fromthe monomers of formulae (1), or (6) and (7), and (2); or (1), or (6)and (7), and (3); or (2) and (3); or copolymers derived from the citedmonomers and further ethylenically unsaturated monomers. Thesecopolymers (a) can, optionally, also be mixed with (b₁) homopolymersderived from the monomers of formulae (1), or (6) and (7), or (2) or(3), or also with (b₂) further homopolymers or copolymers. Wheremixtures of copolymers obtained from at least two monomers of formulae(1), or (6) and (7); (2) and (3) are used, the mixture ratio can varywithin wide limits and be about 1:10 to 10:1. More or less the sameratios apply to mixtures of homopolymers which can be additionally used.

The monomers of formula (1) preferably have the formulae ##STR6##wherein R and R₁ are as previously defined, or especially the formulae##STR7## wherein R₁ is hydrogen or methyl and R₃ is alkyl of 1 to 4carbon atoms. The compounds of the following formulae may be cited asexamples: ##STR8##

Preferred substituents R₃ are methyl and ethyl. Particularly suitablecompounds of formulae (2) and (3) are those of formulae ##STR9## whereinR₁ is hydrogen or methyl, R₄ is alkyl of 1 to 4 carbon atoms, preferablymethyl or ethyl, and m is an integer from 6 to 15, for example from 6 to10 (m₁) and from 10 to 15 (m₂), as indicated for example in thefollowing formulae ##STR10##

Examples of suitable comonomer components for the manufacture ofcopolymers derived from the monomers of formulae (1) to (3), and alsofor obtaining the further homopolymers which are not derived from themonomers of formulae (1) to (3), are:

(a) vinyl esters of organic acids, for example vinyl acetate, vinylformiate, vinyl butyrate, vinyl benzoate,

(b) vinyl alkyl ketones, such as vinyl methyl ketone,

(c) vinyl halides, such as vinyl chloride, vinyl fluoride, vinylidenechloride,

(d) derivatives of the acrylic acid series, such as acrylic nitrile oracrylic amide and preferably derivatives thereof which are substitutedat the amide nitrogen, for example N-methylolacrylic amide,N-methylolacrylic amide alkyl ethers, for example methylolacrylic amidemonomethyl ether, N,N-dihydroxy-ethylacrylic amide, N-tert. butylacrylicamide and hexamethylolmelamine triacrylic amide, and

(e) α,β-unsaturated mono- or dicarboxylic acids containing 3 to 5 carbonatoms and esters thereof, for example acrylic acid, methacrylic acid,α-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, oritaconic acid and esters thereof with mono- or dialcohols containing 1to 18 carbon atoms, epoxides or phenols, for example ethyl acrylate,methylmethacrylate, glycidyl acrylate, butylacrylate, isobutylacrylate,acrylic acid monoglycol ester, dodecylacrylate or 2-ethyl-hexylacrylate,3-tolyl-2(1)hydroxypropyl-1(2)-methacrylate or2(1)-phenylphenolsulphone-1(2)-hydroxypropylmethacrylate.

Polymerisable olefins, such as isobutylene, butadiene or2-chlorobutadiene or also styrene can also be used.

It is preferred to use acrylic acid, methacrylic acid, the estersthereof with 1 to 18, especially with 1 to 8, carbon atoms in the estermoiety, for example methylmethacrylate, isobutylacrylate,2-ethylhexylacrylate, as well as acrylic amide and methacrylic amide,which can be N-methylolated and optionally etherified, for exampleN-methylolacrylic amide, N-methylolacrylic amide methyl ether.

The manufacture of the polymers by homo- or copolymerisation is effectedby conventional methods, for example preferably by polymerisation inaqueous emulsion or also by solvent polymerisation in a solvent suitablefor this purpose, for example acetone, benzene, sym. dichloroethane,ethyl acetate or trifluoromethylbenzene.

The polymerisation is effected advantageously with the application ofheat, preferably to the boiling temperature of the solvent, andaccompanied by the addition of peroxide or other catalysts which formfree radicals and which are soluble in the reaction medium, for examplebenzoyl peroxide, lauroyl peroxide, α,α'-azobisisobutyrodinitrile orpotassium sulphate or in the presence of redox systems, for examplepotassium peroxide disulphate/sodium bisulphite or ferrosulphate. In themanufacture of copolymers, the monomers can be used in thepolymerisation reaction in any desired quantity ratios. In themanufacture of copolymers from, for example, monomer components, themolar ratio can be for example 1:10 to 10:1, preferably 1:5 to 5:1.

Depending on the nature of the polymerisation conditions and of themonomeric starting materials used, the polymer compounds are obtained inthe form of viscous solutions or of emulsions.

The polymerisation is preferably carried out within a reaction time thatis so chosen that a virtually quantitative conversion of the monomerinto the polymer is attained. The maximum reaction time depends on thecatalyst used and the polymerisation temperature and also on otherconditions, but it is generally in the range of 0.5 to 24 hours.

The polymerisation temperature depends in turn on the chosen catalyst.In the case of emulsion polymerisation in aqueous medium it is usuallyin the range of 20° to 90° C. preferably 40° to 80° C. Wherever possiblethe polymerisation is carried out at atmospheric pressure.

In emulsion polymerisation the monomer or monomers to be polymerised arepolymerised jointly in an aqueous solution of an emulsifier, whererequired under nitrogen.

The concentration of the polymerisation catalyst is usually between 0.1and 2%, referred to the weight of the monomers.

Suitable emulsifiers are cationic, anionic or nonionic surface-activeagents. The hydrophobic constituent of the emulsifier can be ahydrocarbon or a fluorinated hydrocarbon.

Suitable cationic emulsifiers are, for example, quaternary ammoniumsalts or amine salts which contain at least one long-chain alkyl orfluoroalkyl group, or a benzene or naphthalene group which is highlysubstituted by alkyl to yield the hydrophobic constituent.

Further suitable emulsifiers are the non-ionic surfactants in which thehydrophilic constituent is a poly(ethoxy) group and the hydrophobicconstituent is either a hydrocarbon or a fluorinated hydrocarbon group,e.g. the ethylene oxide condensates of alkylphenols, alkanols,alkylamines, alkylthiols, alkylcarboxylic acids, fluoroalkylcarboxylicacids, fluoroalkylamides and the like. Anionic emulsifiers are, forexample, the sulphuric acid or phosphoric acid esters of the citedethylene oxide condensates of long-chain alkylphenols, fatty alcohols,and fatty amines.

In the solvent polymerisation, the monomer or monomers are dissolved ina suitable solvent, such as fluorinated solvents, for examplehexafluoroxylene, benzotrifluoride, or mixtures thereof with acetoneand/or ethyl acetate, and polymerised in a reaction vessel with theaddition of initiators, such as azobisisobutyronitrile or other azoinitiators, in concentrations of 0.1 to 2%, at 40° to 100° C.,optionally under nitrogen.

Preferred solvents are hexafluoroxylene, benzotrifluoride or fluorinatedhydrocarbons.

In the compounds of formula (4) [component (b₃)], which can, optionally,be used in the method of application of the present invention, thesubstituent R' is a straight-chain or branched alkyl radical of 1 to 18carbon atoms, preferably of 1 to 4 carbon atoms, for example methyl,ethyl, propyl, isopropyl, butyl or isobutyl.

Examples of further alkyl radicals are: amyl, hexyl, octyl, decyl,dodecyl, myristyl, palmityl or stearyl. The substituent R₂ ' is hydrogenor the alkyl radical C_(n) H_(2n+1) and n is an integer from 1 to 24, inparticular from 6 to 24 and preferably from 6 to 18 or 8 to 18.

Preferred compounds of formula (4) are those, for example, of formula##STR11## wherein R₅ is alkyl of 1 to 4 carbon atoms, R₁ is hydrogen ormethyl, R₆ is hydrogen, methyl or the radical C_(n).sbsb.1H_(2n).sbsb.1₊₁ and n₁ is an integer from 6 to 24, in particular from 6to 18.

Particularly suitable compounds are also those of formula ##STR12##wherein R₁ and R₅ are as defined hereinbefore and n₂ is an integer from6 to 18, in particular from 8 to 18.

The compounds of formula (4) are obtained, for example, by reactingmethylolated-β-(dialkylphosphone)-propionic acid amides of formula##STR13## wherein R' and R₁ are as defined hereinbefore, with monoalkyl-or dialkylamines which contain 1 to 24 carbon atoms in the alkyl moiety,at elevated temperature.

The compounds of formulae (19) and (20) are also obtained in analogousmanner.

The methylolated β-(dialkylphosphone)-propionic acid amides of formula(21) used as starting compounds are obtained by known methods, forexample by addition of dialkylphosphites to (meth)acrylic amides andsubsequent methylolation.

The manufacture of the compounds of formula (4) can be effected, forexample, without solvents or in organic solvents, or also in organicaqueous systems, by reacting the cited starting materials at 80° to 120°C. The reaction time can be about 3 to 4 hours. Suitable solvents are,for example, halogenated hydrocarbons, such as tetrachloromethane,perchloroethylene, trichloroethylene, ethers, for example dioxan, orconventional aromatic solvents, for example benzene, toluene or xylene.The solvents can contain up to 20% of water, referred to their volume.

The compounds of formula (5) [component (b₄)], which are optionallyused, preferably have the formulae ##STR14## wherein R" is as definedhereinbefore, n₁ is an integer from 6 to 24 and n₂ is an integer from 6to 18 or 12 to 18, and R₇ is hydrogen, methyl or C_(n).sbsb.1H_(2n).sbsb.1₊₁.

Examples of compounds of formula (5) are ##STR15## wherein R₃ ' and nare as defined hereinbefore, R₈ is hydrogen, methyl or C_(n).sbsb.3H_(2n).sbsb.3₊₁ and n₃ is an integer from 8 to 18.

The compounds of formulae (5) and (23) to (30) are obtained by knownmethods by addition of formaldehyde to succinimides, maleinimides orlactams and subsequent reaction with monoalkyl- or dialkylamines whichcontain 1 to 24 carbon atoms in the alkyl moiety. Examples of amines arelaurylamine (of 12 carbon atoms) and cetylamine (of 16 carbon atoms),and also dilaurylamine, distearylamine (of 18 carbon atoms) anddi-2-ethylhexylamine.

The preparations or compositions for carrying out the method ofapplication of the invention, which are in the form of organic solutionsor emulsions, contain as a rule 1 to 30 percent by weight of

(a) at least one copolymer derived from at least two of the monomers offormulae (1) to (3), or of a copolymer of the indicated monomers andfurther ethylenically unsaturated monomers, optionally in admixture withat least one of the components

(b₁) a homopolymer of the monomers (1) to (3),

(b₂) a further homopolymer or copolymer,

(b₃) a compound of formula ##STR16## wherein R' is straight-chain orbranched alkyl of 1 to 18 carbon atoms, R₁ is hydrogen or methyl, R₂ 'is hydrogen or C_(n) H_(2n+1) and n is an integer from 1 to 24, and (b₄)a compound of formula ##STR17## in which A is --CH₂ CH₂ --, ##STR18## R₃' is hydrogen or C_(n) H_(2n+1) and n is an integer from 1 to 24.

The indicated percentages by weight refer to the total weight of thepreparation or composition. The total amount of polymers in thepreparations should therefore not exceed 30 percent by weight,preferably about 20 percent by weight, whereas the amount ofhomopolymers or copolymers or of the compounds of components (b₁) to(b₄), if they are used, can be 1 to 10 percent by weight.

The preparations for providing synthetic organic material with anantistatic and dirt repellent finish therefore contain, for example, 1to 30, in particular 1 to 20 and preferably 1 to 10, percent by weightof at least one copolymer (a), and optionally 1 to 10, preferably 1 to5, percent by weight of components (b₁) to (b₄). The amount of copolymer(a) is preferably 75 to 100 percent by weight, so that components (b₁)to (b₄) (polymeric or monomeric compounds) are used in amounts of 25 to0 percent by weight.

Suitable types of synthetic organic textile material that can be treatedwith the monomeric or polymeric compounds are those, for example,obtained from polyamides, polyesters, polyacrylonitrile or polyolefins.It is also possible to finish with advantage blends of these materials,optionally together with other fibres, for example cotton or wool. Thetextiles can be in the form of threads, fibres, flocks, non-wovens,woven or knitted fabrics or of piece goods, for example floor coverings,or other domestic textiles, such as upholstery fabrics, furnishingmaterials, curtains or wall coverings. The textile materials can beundyed or dyed by known methods.

The preparations or compositions which contain the monomeric orpolymeric compounds can be applied to the substrate in conventionalknown manner at room temperature or also at elevated temperature, forexample at 20° to 40° C. They can also contain further additivescustomarily used in textile finishing. The pH-value of the preparationscan be about 2 to 10, preferably 5 to 8.

The substrates can be treated with solutions or emulsions of thepolymers or of the indicated mixtures. The emulsions are prepared byadding customary and known surface-active assistants (emulsifiers).

Fabrics can be impregnated, for example, by the exhaustion process or ona padder that is coated with the preparation at room temperature. Theimpregnated material is subsequently dried at 80° to 200° C., preferablyat 120° to 160° C. The fixation on the substrates can be effected, ifdesired, in the presence of conventional catalysts that split off acid,for example magnesium chloride or zinc nitrate.

Further methods of application are, for example, spraying, brushingroller coating or slop-padding. The compounds of the present inventionare applied to the substrate in amounts of 0.1 to 10, preferably of 0.5to 5, percent by weight.

The textile material finished according to the invention is antistatic,i.e. it releases no troublesome electrical discharges on being touchedor walked on. The antisoiling effect and also the fastness to rubbingand light and the soft handle are not impaired by the finish.

The finish also has good permanency, i.e. it is resistant to washes withconventional household detergents or to cleaning with customary organicsolvents. Carpeting materials, for example, can be repeatedly brushed,vacuum cleaned or shampooed without any impairment of the finishingeffects.

The following Manufacturing Directions and Examples illustrate thepresent invention in more detail without implying any restriction towhat is described therein. The parts and percentages are by weightunless otherwise indicated.

Manufacturing Directions

1a) 211 g (1 mole) of N-methylol-β-methoxyphosphonopropionic acid amideare dissolved in 50 ml of water and the solution is treated with 85 g(0.1 mole) of methacrylic amide and 0.2 g of hydroquinone monomethylether. The reaction solution is adjusted to a pH of 3 with 1 ml ofconcentrated hydrochloric acid and subsequently stirred for 6 hours at50° C. Upon termination of the reaction, the reaction solution isadjusted to pH 7 with 2 ml of normal sodium hydroxide solution andfiltered, to give 340 g of a 84% solution of the compound of formula##STR19## in 100% yield.

Analysis: calculated: P 11.0 found: P 11.0

Mass spectrum: M = 278 (theory: 278).

1b) Example 1a) is repeated with acrylic amide to give the compound offormula ##STR20## in 98% yield.

Analysis: calculated: P 11.74 found: P 11.6

Mass spectrum: M = 264 (theory: 264).

(2) 133.5 g (0.5 mole) of N-methylol-β-diisopropoxyphosphonopropionicacid amide are reacted with 35.5 g (0.5 mole) of acrylic amide or 42.5 g(0.5 mole of methacrylic amide as in Direction 1a), to give thecompounds of formulae ##STR21## in 100% yield. (3) 119.5 g (0.5 mole) ofN-methylol-β-diethyloxyphosphonopropionic acid amide are reacted with35.5 g (0.5 mole) of acrylic amide as in Direction 1a), to give thecompound of formula ##STR22## in 100% yield.

Analysis: calculated: P 10.6 found P 10.3.

(4) 1 g of hydroquinone monomethyl ether and 101 g (1 mole) ofmethylolacrylic amide are dissolved in 249 g of triethylphosphite. Thereaction mixture is heated to 100° C. A rapid rise in temperature to140° C. ensures and ethanol and triethylphosphite distill off. After thetemperature has fallen again to 100° C. after 2 hours, excess ethylalcohol and unreacted triethylphosphite are distilled off from thereaction mixture in vacuo to give 220 g of the compound of formula##STR23## in 100% yield.

Analysis: calculated: C 43.4 H 7.3 N 6.3 P 14.0 found: C 43.4 H 7.6 N5.9 P 14.0

(5) 85 g (1 mole) of methacrylic amide and 0.2 g of hydroxyquinonemonomethyl ether are dissolved in 1000 ml of benzene. To this solutionare added 30 g of para-formaldehyde. The solution is then warmed to 40°C. and a solution of 105 g (1 mole) of diethanolamine in 300 ml ofbenzene is added in the course of about 2 hours. The reaction mixture isthen kept for a further 5 hours at 60° C. Upon termination of thereaction, the resultant compound precipitates as lower phase. It isisolated and freed from residual solvent, to give 178.5 g of a lightyellow viscous compound of formula ##STR24## in 88.9% yield.

Analysis: calculated: N 13.85 found: N 13.4.

(6) 165 g (1 mole) of 2-glycidyltoluene and 3 g of sodium acetate (dry)are dissolved in 500 ml of ethyl acetate. To this solution are added 86g (1 mole) of methacrylic acid, stabilised with 0.1 g of hydroquinonemonomethyl ether and dissolved in 100 ml of ethyl acetate. After a 5hour reaction at 50° C. the reaction mixture is cooled to roomtemperature and then filtered. The solvent is subsequently distilled offat 50° C. in vacuo, to leave as residue 224.6 g of the compound offormula ##STR25## in 89.8% yield.

Analysis: calculated: C 70.8 H 7.3 found: C 69.9 H 7.4

The compound contains no epoxide groups.

(7) 23.4 g (0.1 mole) of phenylphenolsulphone (mixture of o- andp-phenylphenolsulphone) and 1 g of sodium acetate are dissolved in 50 mlof ethyl acetate. To this solution is added a solution of 14.2 g (0.1mole) of glycidyl methacrylate (stabilised with 0.1 g of hydroquinonemonomethyl ether) in 20 ml of ethyl acetate. After it has reacted for 12hours at 50° C., the reaction mixture is cooled to room temperature andthen filtered. The solvent is subsequently distilled off at 50° C. invacuum to leave as residue 36.5 g of the compound of formula ##STR26##in 97% yield.

Analysis: calculated: C 60.6 H 5.3 S 8.5 found: C 58.4 H 5.3 S 9.3

The compound contains no epoxide groups.

(8) 33.4 g (0.1 mole) of the compound of formula (103) and 21 g (0.1mole) of the compound of formula (106) are emulsified in 214 ml of waterin the presence of 0.2 g of sodium lauryl sulphate as emulsifier. Thepolymerisation is initiated by adding 0.1 g of potassium persulphate andthen carried out at 72° C. After 5 hours 0.1 g of potassium persulphateis again added and the polymerisation is terminated after a further 3hours, to give 238 g of a colourless polymer solution of low viscosity(solids content=18.4), corresponding to a polymer yield of 90%.

(9a) 33.4 g (0.1 mole) of the compound of formula (103) and 48.2 g (0.1mole) of ω-methoxypolyethylene glycol acrylate (molecular weight ˜ 482)are emulsified in 635 ml of water in the presence of 7.2 g of sodiumlauryl sulphate. The polymerisation is initiated by addition of 0.2 g ofpotassium persulphate and then carried out at 75° C. After 4 hours 0.2 gof potassium persulphate is again added and the polymerisation isterminated after a further 3 hours, to give 710 g of a viscous,colourless polymer emulsion (solids content: 15.5%).

Polymer yield: 96.5%.

The following copolymers are obtained by carrying out the procedure ofDirection 9a):

                                      Table 1                                     __________________________________________________________________________                         polymer                                                                             solids content                                                                        polymer                                    No.                                                                              monomer I                                                                              monomer II                                                                             yield in g                                                                          in %    yield in %                                 __________________________________________________________________________    9b 100.2 g (0.3 mole)                                                                     48.2 g (0.1 mole)                                                                      1140  12.8    94.8                                          compound (103)                                                                         MPA.sub.1                                                         9c 33.4 g (0.1 mole)                                                                      144.6 g (0.3 mole)                                                                     1300  13.4    95.7                                          compound (103)                                                                         MPA.sub.1                                                         9d 165.5 g (0.5 mole)                                                                     48.2 g (0.1 mole)                                                                      1420  14.0    93.3                                          compound (103)                                                                         MPA.sub.1                                                         9e 139 g (0.5 mole)                                                                       48.2 g (0.1 mole)                                                                      1250  13.6    90.7                                          compound (101a)                                                                        MPA.sub.1                                                         9f 146 g (0.5 mole)                                                                       48.2 g (0.1 mole)                                                                      1300  13.7    91.3                                          compound (102)                                                                         MPA.sub.1                                                         9g 132 g (0.5 mole)                                                                       48.4 g (0.1 mole)                                                                      1192  16.02   97.5                                          compound (101b)                                                                        MPA.sub.1                                                         9h 44.2 g (0.2 mole)                                                                      19.3 g (0.04 mole)                                                                      456  14.6    95.7                                          compound (105)                                                                         MPA.sub.2                                                         __________________________________________________________________________

                                      Table 2                                     __________________________________________________________________________                                               solids                                                                  polymer                                                                             content                                                                             polymer                      No.                                                                              monomer I                                                                              monomer II                                                                             monomer III                                                                            monomer IV                                                                           yield (g)                                                                           %     yield (%)                    __________________________________________________________________________    9i 528g(2mole)                                                                            193g(0.4mole)                                                                          15g(0.13mole)                                                                          --     4524  15.8  96.3                            compound(101b)                                                                         MPA.sub.1                                                                              MAME                                                     9k 80g(0.25mole)                                                                          31.4g(0.065mole)                                                                       10g(0.087mole)                                                                         --     805   12.72 95.0                            compound(102)                                                                          MPA.sub.1                                                                              MAME                                                     9l 52.8g(0.2mole)                                                                         19.3g(0.04mole)                                                                        4.5g(0.02mole)                                                                         --     678   10.0  93.4                            compound(101b)                                                                         MPA.sub.1                                                                              compound(107)                                            9m 52.8g(0.2mole)                                                                         1903g(0.04mole)                                                                        15.04g(0.04mole)                                                                       --     734   10.7  98.4                            compound(101b)                                                                         MPA.sub.1                                                                              compound(108)                                            9n 52.8g(0.2mole)                                                                         48.4g(0.1mole)                                                                         10.4g(0.1mole)                                                                         --     771   13.5  93.7                            compound(101b)                                                                         MPA.sub.2                                                                              styrene                                                  9o 44.2g(0.2mole)                                                                         19.3g(0.04mole)                                                                        1.15g(0.01mole)                                                                        --     477   13.8  98.02                           compound MPA.sub.1                                                                              MAME                                                     9p 52.8g(0.2mole)                                                                         48.4g(0.1mole)                                                                         10.4g(0.1mole)                                                                         10.4g(0.01                                                                           805   16.7  88.0                            compound(101b)                                                                         MPA.sub.1                                                                              styrene  mole)meth-                                                                    ylmeth-                                                                       acrylate                                        __________________________________________________________________________     MPA.sub.1 = ω-methoxypolyethylene glycol acrylate [CH.sub.3             O(CH.sub.2 CH.sub.2 O).sub.6-10 COCH=CH.sub.2                                 MPA.sub.2 = ω-methoxypolyethylene glycol acrylate [CH.sub.3             O(CH.sub.2 CH.sub. 2 O).sub.10-15 COCH=CH.sub.2                               MAME = N-methylolacrylic amide monomethyl ether                          

(10a) The procedure of Manufacturing Direction 9a) is repeated using asolution of 10 g of methylolacrylic amide monomethyl ether in 50 ml ofdeionised water after a polymerisation time of 3 hours. After a furtherhour 0.2 g of potassium persulphate is added and the polymerisation isthen terminated after 3 hours, to give 756 g of a viscous, colourlesspolymer emulsion (solids content: 23.2%), corresponding to a polymeryield of 97.8%.

(10b) The procedure of Manufacturing Direction 9a) is repeated using52.8 g (0.2 mole) of the compound of formula (101b), 24.5 g (0.04 mole)of a ω-methoxypolyethylene glycol acrylic acid ester [CH₃ O(CH₂ CH₂O)₁₀₋₁₅ COCH=CH₂ ] and 1.15 g (0.01 mole) of methylolacrylic amidemonomethyl ether, to give 455 g of a viscous, colourless polymeremulsion (solids content: 15.8%).

Polymer yield: 95.5%.

(11) 20.2 g (0.1 mole) of compound (106) and 33.4 g (0.1 mole) ofcompound (103) are dissolved in 180 ml of water and polymerised for 24hours at 50° C. in the presence of 0.2 g of potassium persulphate, togive 226 g of a viscous emulsion which, after filtration, has a solidscontent of 21.4%.

Polymer yield: 93.8%.

A storable emulsion with a pH of 7 is obtained by adding 5 g ofpolyacrylic acid.

(12a) Copolymer of isobutylacrylate/methylmethacrylate/methacrylicamide-N-methylol monomethyl ether. 55.2 g (0.4 mole) of isobutylacrylateare dissolved in 150 ml of water and in the presence of 1 g of sodiumlauryl sulphate. The polymerisation is initiated by addition of 0.1 g ofpotassium persulphate. Then 10 g (0.1 mole) of methylmethacrylate areadded in the course of 35 minutes and the polymerisation is continuedfor 41/2 hours at 75° C. Then 2 g (0.015 mole) of methacrylicamide-N-methylol monomethyl ether, dissolved in 100 ml water, and 0.2 gof potassium persulphate are added and the polymerisation is brought tocompletion after a further 3 hours at 85° C., to give 314 g of a viscousemulsion with a solids content of 21% (corresponding to a polymer yieldof approx. 100%).

Copolymers are obtained from the following monomers in analogous manner:

(b) 2 parts of isobutylacrylate

1.4 parts of methylmethacrylate

1 part of acrylic acid

(c) 5 parts of isobutylacrylate

1 part of methylmethacrylate

2 parts of methacrylic amide-N-methylol monomethyl ether

(d) 2 parts of isobutylacrylate

1 part of methylacrylate

1 part of acrylic acid.

(13) 105.5 g (0.5 mole) of methylol-β-dimethoxyphosphonopropionic acidamide and 120.5 g of cetylamine (0.5 mole) are dissolved in 1000 ml ofdioxan and the solution is heated for 10 hours to 100° C. (reflux). Thesolvent is subsequently distilled off in a water-jet vacuum to give 224g of a wax-like compound of formula ##STR27## in 99% yield.

Analysis: calculated: N 6.45 P 7.12 found: N 6.22 P 7.52

Mass spectrum: M = 434 (theory: 434).

(14) The procedure of Direction 13) is repeated using 134.5 g (0.5 mole)of stearylamine in place of cetylamine to give 229 g of a wax-likecompound of formula ##STR28## in 99.1% yield.

Analysis: calculated: N 6.06 P 6.70 found: N 5.95 P 6.70

Mass spectrum: M = 462 (theory: 462).

(15) The procedure of Direction 13) is repeated using 92.5 g (0.5 mole)of laurylamine in place of laurylamine to give 175.4 g of a wax-likecompound of formula ##STR29## in 92.8% yield.

Analysis: calculated: N 7.4 P 8.2 found: N 7.3 P 8.7

Mass spectrum: M = 378 (theory: 378).

(16) The procedure of Direction 13) is repeated using 120.5 g (0.5 mole)of di-2-ethylhexylamine in place of cetylamine to give 188.5 g of acompound of formula ##STR30## in 95.7% yield.

Analysis: calculated: N 6.45 P 7.12 found: N 6.22 P 6.4

Mass spectrum: M = 434 (theory: 434).

(17) The procedure of Direction 13) is repeated using 133.5 g (0.5 mole)of methylol-β-diisopropoxyphosphonopropionic acid amide and 134.5 g (0.5mole) of stearylamine to give 235 g of a compound of formula ##STR31##in 96.5% yield.

Analysis: calculated: N 5.04 P 5.97 found: N 5.5 P 6.1

Mass spectrum: M = 518 (theory: 518).

(18) The procedure of Direction 13) is repeated using 133.5 g (0.5 mole)of methylol-β-diisopropoxyphosphonopropionic acid amide and 120.5 g ofhexadecylamine (0.5 mole), to give 235 g of a compound of formula##STR32## in 96% yield.

Analysis: calculated: N 5.71; P 6.31; found: N 5.7; P 6.5.

Mass spectrum: M = 490 (theory: 490).

(19) The procedure of Direction 13) is repeated using 133.5 g (0.5 mole)of methylol-β-diisopropoxyphosphonopropionic acid amide and 260.5 g (0.5mole) of stearylamine, to give 378 g of the compound of formula##STR33## in 98.2% yield.

Analysis: calculated: N 3.63; P 4.02; found: N 3.8; P 3.9.

Mass spectrum M = 770 (theory: 770).

(20) 73.5 g (0.5 mole) of phthalimide are reacted with 15 g (0.5 mole)of formaldehyde and 92.5 g (0.5 mole) of laurylamine in benzene for 10hours at 80° C. as in Direction 13). The solvent is subsequentlydistilled off in a water-jet vacuum.

Yield: 168 g (=97.7%) of the compound of formula ##STR34##

Analysis: calculated: N 8.14 found: N 8.0

Mass spectrum: M = 344 (theory: 344).

(21) 73.5 g (0.5 mole) of phthalimide are reacted with 15 g (0.5 mole)of formaldehyde and 120.5 g (0.5 mole) of cetylamine as in Direction20).

Yield: 198 g (=99%) of the compound of formula ##STR35##

Analysis: calculated: N 7.0; found: N 7.3.

Mass spectrum: M = 400 (theory: 400).

(22) 56.5 g (0.5 mole) of caprolactam are reacted with 15 g (0.5 mole)of formaldehyde and 92.7 g (0.5 mole) of laurylamine as in Direction20).

Yield: 146.6 g (=94.7%) of the compound of formula ##STR36##

Analysis: calculated: N 9.02 found: N 8.75

Mass spectrum: M = 310 (theory: 310).

(23) 56.5 g (0.5 mole) of caprolactam are reacted with 15 g (0.5 mole)of formaldehyde and 92.5 g (0.5 mole) of laurylamine as in Direction20), to give 146.6 g of the compound of formula ##STR37## in 94.7%yield.

Analysis: calculated: N 9.02 found: N 8.75

Mass spectrum: M = 310 (theory: 310).

(24) 73.5 g (0.5 mole) of phthalimide are reacted with 15 g (0.5 mole)of formaldehyde and 285.5 g (0.5 mole) of stearylamine as in Direction20).

Toluene is used as solvent.

Yield: 332 g (=97.1%) of the compound of formula ##STR38##

Analysis: calculated: N 4.4 found: N 4.2.

(25) 56.6 g (0.5 mole) of caprolactam are reacted with 15 g (0.5 mole)of formaldehyde and 120.5 g (0.5 mole) of cetylamine as in Direction20), with toluene as solvent, to give 178 g of the compound of formula##STR39## in 97% yield.

Analysis: calculated: N 7.64 found: N 7.1

Mass spectrum: M = 366 (theory: 366).

(26) 49.5 g (0.5 mole) of succinimide are reacted with 15 g (0.5 mole)of formaldehyde and 92.5 g (0.5 mole) of laurylamine as in Direction20), with toluene as solvent, to yield 115 g of the compound of formula##STR40## in 83.94% yield.

Analysis: calculated: N 9.45; found: -- N 9.2.

(27) 49.5 g (0.5 mole) of succinimide are reacted with 15 g (0.5 mole)of formaldehyde and 120.5 g (0.5 mole) of cetylamine as in Direction20), with toluene as solvent, to yield 176 g of the compound of formula##STR41## in 100% yield.

Analysis: calculated: N 7.95 found: -- N 7.2

(28) 98.5 g (0.5 mole) of laurinolactam are reacted with 15 g (0.5 mole)of formaldehyde and 92.5 g (0.5 mole) of laurylamine as in Direction20), with toluene as solvent, to give 197 g of the compound of formula##STR42## in 100% yield:

Analysis: calculated: N 7.1 found: N 7.5.

(29) the following mixtures of copolymers - obtained according toDirection 9a) - and further monomers are prepared:

    ______________________________________                                                                       solids                                                                        content of                                                       monomeric    the mixture                                    copolymer         compound     in %                                           ______________________________________                                        a)  55.6 g (0.02 mole) of the                                                                       4.4 g (0.01 mole)                                                                          16                                             compound of formula (101a)                                                                      of the compound                                             19.3 g (0.04 mole) of MPA.sub.2                                                                 of formula (109)                                            1.5 g (0.01 mole) of MAME                                                 b)  as a)             4.6 g (0.01 mole)                                                                          15.5                                                             of the compound                                                               of the formula (110)                                    c)  as a)             4 g (0.11 mole)                                                                            16                                                               of the compound                                                               of formula (121)                                        d)  27.8 g (0.1 mole) of the                                                                        4.4 g (0.01 mole)                                                                          10                                             compound of formula (101a)                                                                      of the compound                                             20.2 g (0.1 mole) of the                                                                        of formula (109)                                            compound of formula (106)                                                     20 g (0.2 mole) of methyl-                                                    methacrylate                                                              e)  55.6 g (0.2 mole) of the                                                                        4.4 g (0.01 mole)                                                                          15.5                                           compound of formula (101a)                                                                      of the compound                                             19.3 g (0.04 mole) of MPA.sub.2                                                                 of formula (109)                                        ______________________________________                                    

EXAMPLE 1

The following preparations are prepared and padded on polyamide carpetsat room temperature. The carpets are squeezed out to a weight pick-up of100%. The finished carpets are subsequently dried for 30 seconds at 170°C. Preparations (the parts denote the solids content of the respectivepolymer):

A. 50 g/l of the polymer emulsion of Direction 11)

B. 35.8 g/l of an emulsion consisting of 66.8 parts of the polymerobtained in Direction 8)

56.3 parts of the polymer obtained in Direction 9a), and

67.9 parts of the polymer obtained in Direction 12a)

C. 50 g/l of an emulsion consisting of

60.4 parts of the polymer obtained in Direction 9e) and

121.2 parts of the polymer obtained in Direction 11)

D. 1 part of the copolymer of Direction 12b)

1 part of the copolymer of Direction 9e)

2.5 parts of the copolymer derived from 1 parts of the monomer obtainedin Direction 1a) and 1 part of the monomer obtained in Direction 5)

E. 1 part of the copolymer obtained in Direction 9b)

1.25 parts of the copolymer derived from 1 part of the monomer obtainedin Direction 1a) and 1 part of the monomer obtained in Direction 5)

F. 2 parts of the copolymer obtained in Direction 2c)

1.5 parts of the copolymer obtained in Direction 9e)

2 parts of the copolymer derived from 1 part of the monomer obtained inDirection 1a) and 1 part of the monomer obtained in Direction 5)

G. 1 part of the copolymer obtained in Direction 12c)

1 part of the copolymer obtained in Direction 9e)

1 part of the polymer obtained from the monomer obtained in Direction 5)

1 part of the copolymer obtained in Direction 12d)

H. 1 part of the copolymer obtained in Direction 12d)

1 part of the polymer obtained from the monomer prepared in Direction 5)

1 part of the copolymer obtained in Direction 9e).

The parts referred to in the mixtures D. to H. refer to "parts ofaqueous emulsion with 10% solids content" of the indicated homopolymersor co-polymers. The results are reported in Table III.

                                      Table III                                   __________________________________________________________________________                  A  B  C  D  E  F  G  H                                          __________________________________________________________________________    fastness to rubbing (dry):                                                                  5  5  4  5  4-5                                                                              5  5  5                                            (wet):      4  5  4  4-5                                                                              4-5                                                                              5  4  4-5                                        handle        soft                                                                             soft                                                                             soft                                                                             soft                                                                             soft                                                                             soft                                                                             soft                                                                             soft                                       antistatic effect                                                                           good                                                                             very                                                                             very                                                                             very                                                                             very                                                                             very                                                                             very                                                                             very                                                        good                                                                             good                                                                             good                                                                             good                                                                             good                                                                             good                                                                             good                                       antisoil effect (dry):                                                          treated     3  3  3  3  3  3  3  3                                            untreated   2-3                                                                              2-3                                                                              2-3                                                                              2-3                                                                              2-3                                                                              2-3                                                                              2-3                                                                              2-3                                        __________________________________________________________________________     The fastness to rubbing is evaluated by the rating 1 to 5 (maximum rating     = 5)                                                                          The antisoil effect is evaluated by means of a grey Scale (1 to 5), in        which the highest rating is 5.                                           

EXAMPLE 2

(a) A polyamide carpet is padded at room temperature with the followingpreparations and squeezed out to a weight pick-up of 100%. The finishedcarpet is then dried for 30 seconds at 170° C.

Preparation (the amounts in g/l indicate the solids content):

A. 50 g/l of the mixture consisting of 1 part of the compound of formula(121) and 4 parts of the aqueous emulsion prepared according toDirection 9d) (solids content 10%)

B. 85.5 g/l of the mixture consisting of 20 parts of the emulsion (20g/l) of the compound of formula (109) and 80 parts of the polymeremulsion prepared in Direction 9a)

C. 15 g/l of the mixture according to B.

The following results are obtained:

                  Table IV                                                        ______________________________________                                                           A       B                                                  ______________________________________                                        fastness to rubbing (dry):                                                                         5         4                                                (wet):             4         4                                              handle               soft      soft                                           antistatic effect    very      very                                                                good      good                                           antisoil effect (dry):                                                          treated            4         3-4                                              untreated          3         3                                              ______________________________________                                    

(b) Different fabrics are padded at room temperature with preparation C(15g/l of the mixture according to B), squeezed out and dried asdescribed in a).

The antisoil effect is determined by reflection measurement(determination of the whitening (-) or greying (+) compared withuntreated material).

                  Table V                                                         ______________________________________                                        fibrous material     antistatic                                                                              antisoil                                                                             effect dry                              (wovens)    handle   effect    treated                                                                              untreated                               ______________________________________                                        polyamide   medium   good      6.5(-) 0                                                   soft                                                              polyacrylnitrile                                                                          medium   very good 3.1(-) 0                                                   soft                                                              polyester   medium   very good 3.1(-) 0                                                   soft                                                              polyester/cotten                                                                          medium   --        4.1(+) 0                                       (65/35)     soft               [2.6 (+)                                                                      after 5                                                                       washes]                                        ______________________________________                                    

EXAMPLE 3

Polyamide carpets are padded at room temperature with aqueous (unlessindicated to the contrary) treatment liquors at room temperature to aweight pick-up of 100%. The treated carpets are subsequently dried for10 minutes at 150° C.

The results are reported in Table VI.

Preparations:

1. 50 g/l of an emulsion consisting of

100 parts of the compound of formula (109)

35 parts of the compound of formula (119)

140 parts of the copolymer of Direction 9c)

2. 30 g/l of preparation 1

3. 50 g/l of an emulsion consisting of

10 parts of the compound of formula (114)

128 parts of the copolymer prepared in Direction 9b)

4. 50 g/l of an emulsion consisting of

10 parts of the compound of formula (109)

10 parts of the compound of formula (119)

136 parts of the copolymer prepared in Direction 9e)

5. 50 g/l of an emulsion consisting of

10 parts of the compound of formula (109)

136 parts of the copolymer prepared in Direction 9l)

6. 50 g/l of the emulsion obtained according to Direction 9g)

7. 68.4 g/l of the emulsion obtained according to Direction 9h)

8. 62.4 g/l of the emulsion obtained according to Direction 9i)

9. 78.8 g/l of the emulsion obtained according to Direction 9k)

10. 100 g/l of the emulsion obtained according to Direction 9l)

11. 74.6 g/l of the emulsion obtained according to Direction 9m)

12. 74.6 g/l of the emulsion obtained according to Direction 9n)

13. 72.4 g/l of the emulsion obtained according to Direction 9o)

14. 72.8 g/l of the emulsion obtained according to Direction 9p)

                                      Table VI                                    __________________________________________________________________________                                   electrostatic behaviour                        prepa-                                                                            fastness to rubbing                                                                     colour                                                                            handle                                                                              soil tendency max.charge                              ration                                                                            dry  wet   (compared with untreated material)                                                            resistance Ω                                                                   (volt)                                  __________________________________________________________________________    1   4    4    white                                                                             soft  slighter                                                                             1.7 · 10.sup.11                                                              2-332                                  2   4    3-4  white                                                                             soft  same   1.5 · 10.sup.11                                                             139-297                                 3   5    4-5  white                                                                             as untre-                                                                           as untreated                                                                         8.2 · 10.sup.11                                                              810-1600                                                 ated                                                        4   4-5  4    white                                                                             as un-                                                                              as untreated                                                                         5.9 · 10.sup.10                                                             200-780                                                   treated                                                                             as untreated                                                                         5.9                                            5   4-5  3    as un-                                                                            as un-                                                                              as untreated                                                                         4.4 · 10.sup.10                                                             270-800                                               treated                                                                           treated                                                     6   4,5  4    as un-                                                                            as un-                                                                              as untreated                                                                         2.2 · 10.sup.11                                                             360-899                                               treated                                                                           treated                                                     7   4.5  4.5  as un-                                                                            as un-                                                                              as untreated                                                                         1.2 · 10.sup.11                                                              70-460                                               treated                                                                           treated                                                     8   4.5  4    as un-                                                                            as un-                                                                              as untreated                                                                         7.0 · 10.sup.10                                                             300-1095                                              treated                                                                           treated                                                     9   5    4    as un-                                                                            somewhat                                                                            somewhat                                                                             1.8 · 10.sup.11                                                              750-1430                                             treated                                                                           harder                                                                              stronger                                              10  5    5    as un-                                                                            as un-                                                                              somewhat                                                                             1.1 · 10.sup.10                                                             10                                                    treated                                                                           treated                                                                             stronger                                              11  4.5  4.5  as un-                                                                            softer                                                                              somewhat                                                                             3.5 · 10.sup.10                                                             10                                                    treated   stronger                                              12  5    4.5  as un-                                                                            as un-                                                                              somewhat                                                                             9.6 · 10.sup.10                                                              38-440                                               treated                                                                           treated                                                                             stronger                                              13  5    4.5  as un-                                                                            softer                                                                              somewhat                                                                             2.5 · 10.sup.11                                                              570-1380                                             treated   stronger                                              14  5    5    as un-                                                                            as un-                                                                              somewhat                                                                             2.9 · 10.sup.10                                                              10-200                                               treated                                                                           treated                                                                             stronger                                              __________________________________________________________________________     The resistance [Ω] for untreated material is 10.sup. 13 ; the           maximum charge is approximately 1000 volts.                              

EXAMPLE 4

Polyamide carpets are treated with the mixtures of ManufacturingDirection 29) (in each case 50 g/l of the mixtures, 80 g/l in 29d) as inExample 3. The results obtained are reported in Table VII.

                                      Table VII                                   __________________________________________________________________________    preparation                                                                          29a   29b   29c   29d   29e                                            __________________________________________________________________________    fastness to                                                                   rubbing: dry                                                                         4.5   4.5   4.5   4.5   4.5                                              wet  4     4     4     4.5   4                                              colour as un-                                                                              as un-                                                                              as un-                                                                              as un-                                                                              as un-                                                treated                                                                             treated                                                                             treated                                                                             treated                                                                             treated                                        handle somewhat                                                                            as un-                                                                              as un-                                                                              as un-                                                                              softer                                                softer                                                                              treated                                                                             treated                                                                             treated                                              soil   as un-                                                                              slighter                                                                            as un-                                                                              slighter                                                                            as un-                                         tendency                                                                             treated     treated     treated                                        electro-                                                                      static be-                                                                    haviour:                                                                      resistance                                                                           1.3 · 10.sup.11                                                            2.2 · 10.sup.11                                                            1.8 · 10.sup.11                                                            1.0 · 10.sup.11                                                            6.4 · 10.sup.10                       maximum                                                                              115-380                                                                             1940-3420                                                                            820-1590                                                                            950-1590                                                                            40-360                                        charge                                                                        (volts)                                                                       __________________________________________________________________________

Colour, handle and soil tendency are indicated in comparison withuntreated material.

I claim:
 1. A method of providing synthetic organic fibrous materialwith an antistatic and dirt repellent finish which comprises treatingsaid material with an aqueous or organic solution or emulsion containing1-30 percent by weight of a composition consisting essentially of a 75to 100 percent by weight of a copolymer having a molecular weightbetween about 2,000 and 50,000 of at least two monomers in a ratio ofabout 1:10 to 10:1 and of the formulae ##STR43## or mixtures of suchcopolymers whereinR is straight-chain or branched alkyl of 1 to 8 carbonatoms, R₁ is hydrogen or methyl, R₂ is alkyl of 1 to 6 carbon atoms, mis an integer from 6 to 15 and each of r and s is 1 or 2;or saidcopolymer of at least two of (1), (2) and (3) containing an additionalmonomer in a ratio of about 1:10 to 10:1 and selected from the groupconsisting of vinyl esters of organic acids, vinyl alkyl ketones, vinylhalides, acrylic nitrile or acrylic amide and derivatives thereof, whichare substituted at the amide nitrogen and α,β-unsaturated mono - ordicarboxylic acids containing 3 to 5 carbon atoms and esters thereof;and b.25 to 0 percent by weight of at least one of b₁. a homopolymer of(1), (2) or (3) having a molecular weight of about 2,000 to 50,000; b₂.a homopolymer or copolymer of vinyl esters of organic acids, vinyl alkylketones, vinyl halides, acrylic nitrile or acrylic amide or derivativesthereof which are substituted at the amide nitrogen, or α,β-unsaturatedmono- or dicarboxylic acids containing 3 to 5 carbon atoms or estersthereof, and having a molecular weight between about 2,000 and 50,000;b₃. a compound of the formula ##STR44## wherein R' is straight-chain orbranched alkyl of 1 to 18 carbon atoms, R₁ is hydrogen or methyl, R₂ 'is hydrogen or C_(n) H_(2n+1) and n is an integer from 1 to 24; and b₄.a compound of the formula ##STR45## wherein R" is ##STR46## wherein A is--CH₂ CH₂ --,--CH=CH-- or ##STR47## R₃ ' is hydrogen or C_(n) H_(2n+1)and n is an integer from 1 to
 24. 2. A method according to claim 1,wherein the composition contain at least one copolymer of at least twoof the monomers of formulae ##STR48## wherein m₁ in an integer from 6 to10, or a copolymer of the cited monomers and further ethylenicallyunsaturated monomers.
 3. A method according to claim 1, wherein thecomposition contains at least one copolymer of at least two of themonomers of formulae ##STR49## wherein m₁ is an integer from 6 to 10, inadmixture with at least one compound of the formula ##STR50##
 4. Amethod according to claim 1, wherein the composition contains at leastone copolymer of at least two of the monomers of formula ##STR51##wherein m₁ is an integer from 6 to 10, or a copolymer of the citedmomomers and further ethylenically unsaturated monomers, in admixturewith at least one compound of formulae ##STR52##
 5. A method accordingto claim 1, wherein the monomers of (a) (1), (2) and (3) respectivelyare of ##STR53## wherein R₁ is hydrogen or methyl, R₃ and R₄ are alkylof 1 to 4 carbon atoms and m is an integer from 6 to
 15. 6. A methodaccording to claim 5, wherein the copolymer of (a) is a copolymer of themonomers of formulae ##STR54## wherein m₂ is an integer from 10 to 15.7. A method according to claim 1, wherein the copolymer is (a) is acopolymer of the monomers of formulae ##STR55##
 8. A method according toclaim 1, wherein the copolymer of (a) is a copolymer of the monomers offormulae ##STR56## wherein m₁ is an integer from 6 to
 10. 9. A methodaccording to claim 1, wherein the copolymer of (a) is a copolymer of themonomers of formulae ##STR57## wherein m₁ is an integer from 6 to 10.10. A method according to claim 1, wherein the monomers of (a) (1), and(3) respectively are of the formulae ##STR58## wherein R₁ is hydrogen ormethyl, R₃ and R₄ are alkyl of 1 to 4 carbon atoms and m₁ is an integerfrom 6 to
 10. 11. A method according to claim 1, wherein the compositioncontains copolymers of the monomers of formulae (1) and (2) in admixturewith copolymers of the monomers of formulae (1) and (3) and (3) ofcopolymers of the monomers of formulae (1) and (3) in admixture withcopolymers of the monomers of formulae (2) and (3).
 12. A methodaccording to claim 1, wherein the composition contains copolymers of themonomers of formulae (1) to (3) in admixture with homopolymers of themonomers of formulae (1) to (3).
 13. A method according to claim 1,wherein the additional monomers of (a) and the monomers of (b₂) areacrylic acid, methylmethacrylate, isobutylacrylate, methacrylicamide-N-methylol monomethyl ether, 2-ethylhexylacrylate,3-toyl-2(1)-hydroxypropyl-1(2)-methacrylate and2(1)-phenylphenolsulphone1(2)-hydroxypropylmethacrylate.
 14. A methodaccording to claim 1, wherein the component (b₃) is of the formula##STR59## wherein R₅ is alkyl of 1 to 4 carbon atoms, R₁ is hydrogen ormethyl, R₆ is hydrogen, methyl or the radical C_(n).sbsb.1H_(2n).sbsb.1₊₁ and n₁ is an integer from 6 to
 24. 15. A methodaccording to claim 14, wherein the component (b₃) is of the formula##STR60## wherein n₂ is an integer from 6 to
 18. 16. A method accordingto claim 1, wherein the component (b₄) is of the formula ##STR61##wherein R₇ is hydrogen, methyl or the radical C_(n).sbsb.1H_(2n).sbsb.1₊₁ and n₁ is an integer from 6 to
 24. 17. A methodaccording to claim 16, wherein the component (b₄) is of the formula##STR62## wherein n₂ is an integer from 6 to
 18. 18. A method accordingto claim 1, wherein the component (b₄) is of the formula ##STR63##wherein R₃ ' is hydrogen or C_(n) H_(2n+1) and n is an integer from 1 to24.
 19. A method according to claim 1, which comprises applying theaqueous or organic solution or emulsion to the fibrous material attemperatures of 20° to 40° C.
 20. A method according to claim 1, whichcomprises drying the finished textile material at 80° to 200° C.
 21. Thesynthetic organic fibrous material finished by the method according toclaim 1.